ECS Transactions, 64 (34) 21-29 (2015)

10.1149/06434.0021ecst The Electrochemical Society

Electrochemical Desulfurization of Dibenzothiophene Sulfone in

Acetonitrile/Sodium Nitrate (aq)

M. Gonzlez-Pereaa,*, M. M. Dvila-Jimneza,
M. P. Elizalde-Gonzlezb and P. Ruz-Gutirrezb
a
Facultad de Ciencias Qumicas, b Centro de Qumica, Benemrita Universidad
Autnoma de Puebla, Puebla, Pue. 72570, Mexico

Electrochemical techniques have attracted much attention in the

last decade for oxidative and reductive desulfurization because
they require less drastic conditions of temperature and pressure in
comparison to other processes that are used for desulfurization. It
is known that dibenzothiophene (DBT) can be oxidized
progressively to dibenzothiophene sulfoxide (DBTO) and
dibenzothiophene sulfone (DBTO2). However, it is interesting to
know whether a more complete oxidation of DBTO2 is possible by
electrochemical treatment in a liquid-liquid two-phase system.

Introduction

The methyl-substituted dibenzothiophenes are refractory compounds present in petroleum

and in fossil fuels. These compounds are associated with environmental problems caused
by the emission of SOx as byproducts of the fuel combustion process. Consequently, the
methyl-substituted dibenzothiophene compounds must be removed from fuels in order to
attain satisfactory environmental standards (< 10 ppm). A conventional process of sulfur
removal in fuels is the oxidative desulfurization (ODS), where the sulfur-containing
compounds are initially oxidized to the respective sulfones and are later extracted using a
suitable polar solvent. The procedure can be conducted in liquid phase under mild
conditions and methyl-substituted dibenzothiophenes can be oxidized by the electrophilic
addition reaction of oxygen atoms to its S-oxide or S-dioxide (sulfone). However, the
produced sulfoxides and sulfones are considered an industrial waste that potentially could
be more toxic than their parent dibenzothiophenes when the mineralization is incomplete.
The oxidesulfurization of sulfones has only been achieved under harsh conditions (1). An
efficient technology able to remove sulfur under low temperatures and pressures is the
electrochemical desulfurization (ECDS) technology (2-3). Nevertheless, this technology
is still in its early development stage. In the literature only few works related to oxidation
and reducing of the methyl-substituted dibenzothiophenes are reported (2-9). In this work
we studied the elimination of the SO2 moiety from the dibenzothiophene sulfone
(DBTO2) via electrochemical oxidation.

Experimental

Galvanostatic electrolysis of DBTO2

Background electrolyte solution was prepared by combining 85% (v/v) of ACN

(Honeywell, HPLC grade) with 15% (v/v) of 1.2 M NaNO3 (97.9%, Baker). The
concentration of dibenzothiophene sulfone in the solution was 500 M. The electrolysis

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 ECS Transactions, 64 (34) 21-29 (2015)

was performed in an undivided conventional cell (60 mL) of three electrodes at 25 C.

Two platinum electrodes were used for the electrolysis and Hg/Hg2Cl2 (3M KCl) was
used as reference electrode for monitoring the potential of the anode and the cathode
during the electrolysis. The applied current 32 mA cm-2 was controlled with a regulated
power source (GP-1503DU, EZ digital Co.).

Analysis by infrared spectroscopy (FT-IR)

To obtain infrared spectra, the liquid samples were allowed to evaporate at room
temperature; the resulting solids and the KBr spectroscopic grade (Aldrich) were dried at
60 C during 12 hours. The sample: KBr ratio was 1:200 in the pellets. The IR spectra
were obtained with a resolution of 4 cm-1 applying 64 scans on three different points of
the pellets. Reported IR spectra are the average of the three samples. Also liquid films
were analyzed by IR using a Nicolet spectrophotometer 6700.

Analysis by UV-Vis spectroscopy

Calibration curves and analysis of the products of electrolysis were performed using
an optical probe connected to the spectrometer AvaSpec 2048L. The background
electrolyte (85% ACN + 15% 1.2 M NaNO3) employed for the electrochemical
experiments was used as reference solution for recording the UV-Vis spectra. The kinetic
study of the electrolysis of DBTO2 was conducted in situ with the probe immersed in the
reaction medium and recording several spectra in the range of 0 - 250 minutes.

Analysis of electrolysis products by HPLC-DAD

The electrolysis mixtures were analyzed using an HPLC-DAD equipment of LC

Series 1260 chomatograph equipped with an UV/Vis diode array detector from Agilent
Technologies (Santa Clara, CA. USA). A calibration curve (A = 6.4 + 2.28 C) was
obtained by using six different concentrations of DBTO2 (from 25 to 500 M) with a
correlation coefficient of 0.9995.

Results and discussion

Electrodesulfurization of DBTO2 in a binary solution

After 20 min electrolysis of DBTO2 in acetonitrile-water solution in presence of 1.2 M

NaNO3 at 32 mA cm-2, an immiscible phase with a yellow color (dense phase) appeared
in the reactive mixture (Fig. 1). With the electrolysis time and as a result of the oxidation-
reduction reactions of DBTO2, the yellow color increased and tended to diffuse to the
bottom of the cell forming a dense yellow phase.
Because the applied current density was high with a Ecell = 13.6 V during the
oxidation-reduction reactions of DBTO2, both the decomposition of acetonitrile, the
dissolved water and the electrolyte (Scheme 1) occurred simultaneously.

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 ECS Transactions, 64 (34) 21-29 (2015)

Figure 1. Electrochemical system used for the electrochemical electrolysis of DBTO2

and aspect of the reaction mixture solution after 180 min of electrolysis at 32 mA cm-2.

Scheme 1. Oxidation-reduction process of DBTO2 in the liquid-liquid binary solution

during the electrolysis at 32 mA cm-2 on platinum electrodes.

The decomposition of the electrolytic medium (gas evolution) was observed on

platinum electrodes (10, 11). Pons et al. reported (10) that the electrolysis of acetonitrile
at the platinum surface at high cathodic potential generated hydrogen, methane (traces),
acetamide, tributyl amine and butane. The electrochemical oxidation and/or reduction of
sulfur containing compounds in fossil fuels have been also reported (2, 3, 6, 12). Several
authors described the reduction-oxidation of NO3-/NO2- (13-15). These investigations
demonstrated that the acetonitrile, water content in the solvents and the composition of
the electrolyte played an important role in the oxidation-reduction products of sulfur
containing compounds and in the reaction mechanisms. For this reason we cannot rule
out that species generated as a result of the decomposition of the solution, are also
involved in the electrolysis process of DBTO2. During the electrolysis, the interfacial
accumulation of OH- occurs as a result of the reduction of acetonitrile and dissolved
water in the mixture to H2. The pH of the initial mixture CH3CN-H2O/NaNO3 solution
was 8.44 and after 3 hours of electrolysis at current density of 32 mA cm-2 it was 0.64 for
the less dense phase (Fig. 1) and 13.4 for the yellow phase (Table I).

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 ECS Transactions, 64 (34) 21-29 (2015)

TABLE I. Electrical conductivity and pH values of the different phases obtained by electrolysis of
DBTO2 in 85% ACN + 15% NaNO3 1.2 M
Sample pH Conductivity, mS cm-1

500 M DBTO2 dissolved in 85% ACN + 15% NaNO3 1.2 M 8.4 11.1

Acetonitrile phase after electrolysis 0.6 6.3

Water phase after electrolysis 13.4 97.0

The conductivity of the initial ACN-H2O/NaNO3 binary solution differed greatly from
the values in the two new phases (Table 1). The high conductivity of the yellow phase
after electrolysis indicates that this phase is more polar and that the products of the
oxidation-reduction of DBTO2 are polar compounds. We consider that the yellow phase
(liquid-liquid two-phase system) formed during the electrolysis is due to the shift of the
equilibrium of the initial reactive mixture (ACN 85%: H2O 15%) (16), which changes the
ionic strength of the medium, pH and conductivity (Table 1).
The probable mechanism of electro oxidation-reduction of DBTO2 in an undivided
cell under high anodic-or cathodic conditions is shown in the Scheme 2.

Anode
[O] Anode

DBT DBTO2 Sulfonic

compounds

[H]
Cathode

Scheme 2. Oxidation-reduction mechanism of DBTO2 in the liquid-liquid binary solution

during the electrolysis at 32 mA cm-2 on the platinum electrodes. Adapted from (7).

We consider that the formation of sulfonic compounds occurs on the anode by the
action of radical species formed on the platinum electrode anode according to reactions 1
and 2:

Pt(H2O)
Pt(OH) + H+ + e- [1]

Pt(OH) + DBTO2
Sulfonic compounds [2]

Characterization of the oxidized products

UV-Vis analysis. The oxidation-reduction reaction of the DBTO2 during the

electrolysis in an undivided cell was monitored in-situ in the less dense phase (near to the
anode) by UV-Vis spectroscopy (Fig. 2). The UV-Vis spectra in the low density phase
(Fig. 1) during the electrolysis of the DBTO2 exhibited progressive decrease at the
distinctive absorption bands at max= 270 nm and max = 318 nm (Fig. 2).

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 ECS Transactions, 64 (34) 21-29 (2015)

2.0
2.0
270 nm
1.6

Absorbance , a. u.
Absorbance , a. u.
1.5 1.2 270 nm

318 nm

0.8 358 nm

0.4
1.0 318 nm
0.0
0 50 100 150 200
t , min
0.5 358 nm

0.0

300 400 500

, nm
Figure 2. Variation of the UV-Vis spectra with the electrolysis time of DBTO2. Insert:
Dependence between absorbance at 270 nm, 318 nm and 358 nm with the electrolysis
time. (-----) Reference solution.

The results showed that the bands of DBTO2 at 270 and 318 nm were reduced in a 7
and 61 % respectively after 180 min of electrolysis and after 250 min electrolysis (not
shown here) in a 44 and 73 %, respectively. Simultaneously, with the decrease of the
absorbance at 270 and 318 nm a band in the region within 300 and 400 nm was observed.
After 250 min of electrolysis (Fig. 3) a broad band in the region of 300 to 500 nm was
notorious in the UV-Vis spectra of the less dense phase.
2.0
270 Mixture solution
344 Low density phase
Yellow phase
Absorbance , u. a.

1.5

1.0
318

0.5

0.0

200 300 400 500 600

, nm

Figure 3. UV-Vis spectrum of DBTO2 dissolved in the binary solution (), of the less
dense phase (---) and of the yellow phase (), both containing the products generated by
electrolysis.

Kinetics of the electrochemical oxidation of DBTO2. As shown in Figure 2, DBTO2

slowly decomposed during the electrolysis at 32 mA cm-2. The kinetics of the reaction
and the conversion percent of DBTO2 in the reaction mixture ACN:H2O during the time
electrolysis could be followed conveniently by monitoring the DBTO2 absorption band at
318 nm (Fig. 4), whereas the decrease of the band at 270 nm was not linear with time (see
insert in Fig. 4). Hence, the decomposition kinetics of DBTO2 was followed from the
calibration curve at max = 318 nm.

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 ECS Transactions, 64 (34) 21-29 (2015)

2
270 nm 2.0

270 nm
1.5

Absorbance , a. u.

Absorbance , a. u.
1.0

0.5
1 318 nm

0.0
0 200 400 600
318 nm [M]

250 300 350 400 450 500

, nm
Figure 4. UV-Vis spectra of DBTO2 at different concentrations dissolved in 85% ACN +
15% NaNO3 1.2M. Insert: Calibration curves of DBTO2 at two different wavelengths.

A plot of ln (Ct/Co) versus reaction time displayed a linear relationship that confirmed
the pseudo-first order reaction kinetics (Fig.5). The rate constant for DBTO2 oxidation
reaction was determined to be 4.8 x10-3 min-1. The DBTO2 exhibited a conversion of
70 % after a 250 min electrochemical reaction.
100
0.0
80

% conversion
ln [ Ct / Co ]

-0.4 60

40
-0.8
20

-1.2 0

0 100 200 300

t , min.
Figure 5. Conversion rate and pseudo- first order kinetics for the electrolytic degradation
of DBTO2 followed through the variation of the absorbance at max = 318 nm.

FT-IR analysis of the electrolysis products. The dense yellow phase (see Fig.1) was
subjected to FTIR analysis after electrolysis. As shown in Figure 6, the absorption bands
at 1288 cm-1 and 1168 cm-1 typical of the sulfone group in DBTO2 (Fig. 6a) are absent in
the IR spectrum of the dense phase (Fig. 6b) after electrolysis. The vibration bands of the
benzene ring at 1452 cm-1 and 1480 cm-1 in the DBTO2 also disappeared after electrolysis.
In contrast, the new peaks shown in the IR sample after electrolysis (Fig. 6 b) reflected
the formation of different compounds as consequence of the oxidation-reduction process
that occurred during the electrolysis. Namely, the absence and the emergence of
absorption peaks manifested the destruction of the sulfonyl group of the DBTO2. This
indicated that the DBTO2 was degraded during electrolysis.

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100

90

730
(a)

% Transmittance
80

758
1288
1166
2096
70

779
100

1151
2179

465
2426

654
835
1771

1270
50

1674
3444
(b)

1385
1574
0
4000 3000 2000 1000
-1
Wavenumber , cm
Figure 6. IR spectra of DBTO2 (a) and the yellow phase obtained by electrolysis of
DBTO2 (b).

The bands associated with the inorganic species NO3- and OH-, present in the yellow
phase of the reaction mixture (ACN-H2O) after electrolysis, explain the high conductivity
of this phase and its high pH value.

Analysis of electrolysis products by HPLC-DAD. In figure 7 the percentage of

DBTO2 removed from the reaction mixture ACN-H2O during 6 hours of electrolysis is
shown. The removal of DBTO2 was of 94 % after 6 hours of electrolysis and after 3 hours
it was lower (75 %). This percentage of conversion of DBTO2 determined by liquid
chromatography was identical to that obtained by UV-Vis analysis (73 %).
60
(a) DBTO
2
Absorbance, au

30

P1 P2
0
0 5 10 15
Retention time, min
100 (b) P1
Relative content, %

P2
50

DBTO
2
0
0 120 240 360
Reaction time, min
Figure 7. (a) Chromatogram of less dense phase formed after 6 h of electrolysis of
DBTO2 500 M at 32 mA cm-2; (b) percent of the formed products and of the removed
DBTO2 from the reaction solution.

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 ECS Transactions, 64 (34) 21-29 (2015)

Figure 7 also shows the formation of the products P1 and P2 after electrolysis. The
chromatograms for the initial DBTO2 and for the yellow dense phase at 270 nm after
electrolysis at 32 mA cm-2 are presented in the Figure 8a and 8b, respectively. The
chromatograms reveal three main products formed by electrolysis, whereby their short
retention time in the reversed-phase chromatographic system point out their high polarity.
The peaks P2 and P3 exhibited well-defined UV-Vis spectra, which informed about the
aromatic moieties, as it can be seen in Figure 8b. Studies by LC-ESI-(Qq)-TOF-MS,
MS/MS and GC-MS are in curse for the identification of the electrolysis products.

100 (a)

500 233

50 A bsorbance , au 268
317
0
200 300 400
A bsorbance , au

, nm

0
P2 500
200 (b) P1

270
0
3000 222
239 P2

100 0
355

3000

P3 P3

303
P1 0
200 300 400
, nm
0
0 2 4 6 8 10
Retention time , min
Figure 8. Chromatograms of (a) DBTO2 before electrolysis; (b) the dense yellow phase
after 180 min electrolysis at 32 mA cm-2.

Conclusions

The DBTO2 oxidation in an undivided cell using a binary solution ACN/NaNO3(aq) as

electrolytic medium produced polar compounds. During the electrolysis of DBTO2, the
decomposition of the acetonitrile and water also occurred on the platinum electrodes.
These reactions lead to the formation of a liquid-liquid interface with different polarity,
pH and conductivity values. The formation of two phases with different polarity during
the electrolysis promotes the diffusion of the more polar DBTO2 products to the polar
phase. In this way, the use of the binary solution for the oxidation of DBTO2 leads

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simultaneously to the separation in situ of the oxidation products without subsequent

extraction.

Acknowledgements

This work was supported by the following research projects: CONACyT CB-2008-01-
100439, and INFR-123779-2009. We thank the financial funding of the university
(VIEP-BUAP).

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